technologies for carbon capture in oil refineries

WEC Italia – Cattura e Stoccaggio della CO2 (CCS)

Roma, October 18, 2011

Technologies for Carbon Capture Technologies for Carbon Capture in Oil Refineriesin Oil Refineries

Ivano MiraccaIvano MiraccaSaipem s.p.a.Saipem s.p.a.

Technologies for Carbon Capture in oil refineries Roma, Oct. 18, 20112

Saipem HighlightsLeading Global EP(I)C General Contractor

Designed and built: Over 90 grass roots complexes,

1,700 process units

Over 120,000 km of land pipelines,sealines and trunklines

In the last decade, more than 100offshore EPIC projects, includinggroundbreaking deepwater achievements

Drilled over 7,300 wells of which 1,800 offshore

Distinctive ‘frontier focus’ inOil & Gas industries

Full service EP(I)C provider

Key local employer and investorin strategic markets

Most modern, technologicallyadvanced offshore construction fleet

High quality drilling player onshore and in niches offshore

2010 Revenues 11.2 B€ End-of-2010 Backlog 20.5 B€

40,000 employees, of which 7,000 Engineers & Project Managers

Operating in more than 70 countries,more than 50 permanent establishments,employees from 122 nationalities


Saipem Experience on Carbon Capture and Sequestration (CCS)

SAIPEM has substantial know-how and experience in the entire CO2 capture, transportation and storage chain acquired providing engineering services to Eni and other O&G companies.

• Pipelines design & construction.

•Environmental impact studies.

• Geomechanical modelling and monitoring

• Well and reservoir modelling, • Environmental and wellbore

integrity monitoring• Environmental impact studies

StorageStorage:

CaptureCapture:• Post combustion (CO2 washing)• Pre combustion (Steam reforming/gasification)• Oxy-firing (Oxygen combustion)• Environmental impact studiesTransportatioTransportationn:

SourceSource


Presentation Summary

Power Station vs. Refinery

Refinery Emission Sources

CO2 Capture in the FCC unit

CO2 Capture in Hydrogen Production

CO2 Capture in Crude Heaters and Steam Boilers

Overall approach


A sense of scale

Power stations are responsible for about 80% of CO2 emissions from stationary sources more than 10 billion tons/year

Refineries are third (after cement production) with about 6% of emissions (0.8 billion tons/year)

This justifies current focus on power production Pressure of law-makers concentrated on power production. At the GHGT-10 conference >90% of capture work was related to capture in

coal-fired power stations

800 MW NGCC Power Station ~ 2.8 MTPY of CO2 500 MW Coal Power Station ~ 3.5 MTPY of CO2

Refinery processing 250,000 bpsd of crude ~ 4.5 MTPY of CO2

Emission for a refinery vary for different crudes, fuels and configuration


Different issues and concerns

POWER STATION REFINERY

Single Source Multiple sources (20 or more stacks )

Fixed CO2 Concentration (4% for NGCC – 12% for coal)

CO2 Concentration variable with source and feedstock

Very fast and drastic changes in workload may be required

Capture operation of the same type than usual refinery operation

Plot plan availability is not necessarily a concern

Plot plan availabilty is a key concern

Additional safety issues mainly related to use of chemicals

Additional safety issues mainly related to use of pure oxygen

CO2 capture introduces new types of processes inside the power

station

Already includes process units using the same techniques than

capture units


Emissions vary for different crudes and refineries

LOW EMISSION REFINERY HIGH EMISSION REFINERY

100,000 BPSD LIGHT CRUDE 100,000 BPSD HEAVY CRUDE

No cracking – No sulfur reduction Complex refinery with many different products

Fuel: Natural Gas Fuel: Fuel Oil

Few Heaters & Boilers (< 12) Many Heaters & Boilers (> 50)

No Hydrogen production Hydrogen production

GHG emissions: < 1.2 MTPY GHG emissions: > 4.8 MTPY

Source: ExxonMobil (2008)


Refinery Carbon Sources

SMR Heaters Co-GenFCC

Regen

Fuel

Reformer Feed

Flue Gas Flue Gas Flue Gas Flue Gas

Air

Two major emitters

CCS will mostly be retrofit, with plot space issues

Multiple capture technologies likely needed

Some easy CO2 but not a lot, since pure CO2 vents from hydrogen plants are disappearing as new PSA-based SMRs are built

Emerging resource (e.g. heavy oil) have larger carbon footprint and will increase emissions.

Power Steam


Typical distributions of emissions

10-15% of emissions are caused by fuel combustion for power generation

35-45% of emissions are caused by fuel combustion in process heaters (furnaces) and steam boilers

30-50% of emissions are single source from chemical units , depending on the refinery process scheme:

Renerator of the Fluid Catalytic Cracking unit for FCC-based refineries

Hydrogen production unit for hydrocracker-based refineries

FCC AND HYDROGEN MAIN SINGLE TARGETS FOR SUBSTANTIAL REDUCTION OF GHG EMISSIONS IN A

REFINERY


Overview of an FCC unit

RISER

Products- Gasoline- LPG- Propene

Feed- VGO- ATRSteam

Air

REGENERATOR

Flue gas

10 – 20 % CO2

A unit processing 60,000 bpsd emits ~ 1,000,000 t/year of CO2


Main technological options

A – Waste Heat BoilerB – SOx scrubberC – Amine UnitD – CO2 compressorE – Dehydration (mol. sieve)F – ASUG – Recycle compressor

Flue-gas A B C D

E

Amine Absorption

CO2

Flue-gas A B

F

D

E

G

99.5% O2

Oxy-combustion

CO2

Recycle

Equipment list

> 99% pure90% recovery

96% pure>99 % recovery


Some comparison among options

Energy consumption is higher for the post-combustion case (typically 2.5-3.5 GJ/ton vs. 1.5-2.5 GJ/ton)

Capital cost is higher for oxy-firing, mainly due to the cryogenic separation (Petrobras, 2008).

CO2 avoidance cost is potentially lower for oxy-firing (Petrobras, 2008)

Post-combustion requires plot plan close to the FCC unit (order of 50x50m). Oxy-firing does not, if 96% CO2 purity is acceptable

Surely not acceptable for EOR (oxygen is the main impurity)

Oxy-firing requires safe location for air separation unit and safety measures for pure oxygen piping.


The CO2 Capture Project (www.co2captureproject.org) is undertaking a field demonstration of FCC regenerator oxy-firing with flue gas recycle.

Tests are taking place at a large pilot unit (33bbl/d of feed) at a Petrobras research complex in Parana state, Brazil.

Main goals of the project are: Test start-up and shut-down procedures Maintain stable operation in oxy-combustion

mode Test different operating conditions and process

configurations Obtain reliable data for scale-up

Source: Project Fact Sheet (www.co2captureproject.org)

The CCP Oxy-combustion FCC Demonstration Run


CO2 Capture in hydrogen production

CO2 Capture in hydrogen production


Steam Methane Reforming

SMRWater Gas

ShiftH2 Purification

(PSA)

NaturalGas

Flue Gas ~ 765 kg CO2/ 1000 Ncu ft H2

Feed

Fuel

Steam

Hydrogen product – 99.9+% purity

Low energy usage compared with previous conventional design (MDEA washing)

All CO2 emitted in the flue gas – low partial pressure- even though ~ 60% is generated inside the process at high pressure

Post-combustion only option with this scheme

AirTail gas

Product


Autothermal Reforming

Syngasgeneration

Water-gasshift

CO2removal

Fuel H2, COCO2, H2O

H2, CO2 H2

CO2H2O

O2

H2O

AirSeparation

Air N2

For large volumes, autothermal reforming (ATR) is generally lower cost than SMR.

For a CO2 constrained enviroment ATR is always lower cost when capture is required.

CO2 avoidance cost 50% lower for ATR/MDEA vs. SMR/PSA

SMR/MDEA avoidance cost is 30% lower than ATR/MDEA, but only process side CO2 is captured (source: Chevron,2008)


CO2 Capture in process heaters & boilers

CO2 Capture in process heaters & boilers


A large percentage of refinery CO2 emissions are generated by the combustion of fuel gas or fuel oil in crude heaters and steam boilers

In a world-scale refinery this emission source may account for more than 2 million tons/year.

Heaters & boilers are widely scattered in size and in refinery location.

Usually a few tens of units, but may be more than 50. May discharge to ten or more stacks located in different zones A single unit may roughly emit from 50,000 to 500,000 tons/year CO2 concentration in flue gas ranging from 4 to 10% vol., depending on

the fuel used

CAN THIS SOURCE BE MITIGATED?

Heaters & Boilers: a peculiar source of CO2


POST-COMBUSTION Very large and long ducts should be constructed to convey all of the

effluents to a centralized post-combustion unit Alternatively several smaller units should be built close to each stack. Cost and lay-out considerations seem to preclude this approach.

PRE-COMBUSTION All of the fuel could be conveyed to a single large-scale ATR unit, producing

hydrogen to be used as fuel for all heaters & boilers No plot space needed near the existing units Retrofit of heaters and boilers may be needed for hydrogen burning.

OXY-FIRING Today a single train of cryogenic air separation may produce up to 4000

tons/day of oxygen, roughly corresponding to 1 MTPY of emitted CO2 Part of the flue gas (> 50%) would be recycled to each unit for combustion

temperature control Air in-leakage would lead to low CO2 purity (~ 80%) making a purification

step necessary before transportation and storage need for local or centralized plot plan

Retrofit of heaters and boilers may be needed for oxy-combustion.

Capture techniques applied to Heaters & Boilers


Overall approach to carbon capture in the refinery

Overall approach to carbon capture in the refinery


The Hydrogen-fired refinery

Heaters Co-GenFCC

Regen

Air

Power Steam

ATR Water-gasshift

CO2removal

Fuel H2, COCO2, H2O

H2, CO2

CO2H2O

O2

H2O

AirSeparation

Air N2

Flue Gas

Hydrogen

CO2-free gas to stack

To hydrotreating


Gas turbines may only burn fuels containing up to 50% of hydrogen Nitrogen from air separation may be used as diluent Advanced burners for 70-85% concentration are under

development and should be available commercially by 2020.

According to vendors, single line ATRs may be built up to about 500,000 Nm3/h of hydrogen. That would be enough for several refineries. Two parallel lines might be alternatively used.

Hydrogen burning in boilers and heaters is technically feasible, but needs to be demonstrated at the tens of MW scale before commercial implementation.

Current limitations to an hydrogen-fired refinery


The Oxygen-fired refinery

SMR Heaters Co-GenFCC

Regen

Fuel

Reformer Feed

Power Steam

ASUAir Nitrogen

Oxygen

Flue gas

O2

Flue gas

CPUCO2

Flue gas


The oxygen-fired refinery would only mitigate FCC, heaters and boilers emissions.

Hydrogen production and power generation would need separate capture

2-4 parallel air separation trains may be needed FCC regenerator oxy-firing still needs to be proven Oxyfiring of boilers already at the demo stage (30 MW)

Oxyfiring of heaters still needs a dedicated development program

Current limitations to an oxygen-fired refinery


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technologies for carbon capture in oil refineries

Technology

capture units

refinery processing

co2 emissions

power steam

capture work

refinery process scheme

mtpy ghg emissions

natural gas complex